JPH11169133A - Sweetener composition comprising aspartame and its derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly pure sweetener composition providing a taste similar to that of sucrose simply, uniformly and in high yield. SOLUTION: This sweetener composition containing aspartame and N-[N-(3,3- dimethylbutyl)-L-α-aspartyl]-L-phenylalaninemethyl ester is obtained by reductive alkylation between aspartame and 3,3-dimethylbutyl aldehyde, wherein the latter is used in the stoichiometric amount or less with the former to partly form N-[N-(3,3-dimethylbutyl)-L-α-aspartyl]-L-phenylalaninemethyl ester from aspartame, separating the reaction solution from the reducing agent, crystallizing the solution, and collecting the separated crystal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sweet substance aspartame (APM) and N- [N- (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine methyl ester [N- (3,3 -Dimethylbutyl) -A
PM] and a method for producing a sweetener composition and the sweetener composition.

[0002]

BACKGROUND OF THE INVENTION In recent years, with the sophistication of dietary habits, obesity due to excessive sugar intake and various diseases associated therewith have become a problem, and the development of a low-calorie sweetener instead of sugar has been desired. . AP with excellent safety and sweetness
M is widely used as a sweetener, but has some problems in stability. Therefore, as one of attempts to slightly improve the stability and the sweetness intensity, compounds in which an alkyl group has been introduced into the amino group of aspartic acid of APM have been studied. Among them, N- (3,3-dimethylbutyl) has been studied. ) -AP
The fact that the sweetness factor of M is extremely high is described in French Patent 269.
7844. As a method for producing N- (3,3-dimethylbutyl) -APM, A-
A method of reductively alkylating PM with sodium cyanoborohydride in the presence of 3,3-dimethylbutyraldehyde (FR26997844), or a method of converting APM to 3,3-dimethyl in a water-methanol mixed solvent having a pH of 4.5 to 5. Method for reductive alkylation using platinum carbon as a catalyst in the presence of butyraldehyde (WO95 / 3068)
9) is known, but when the reaction is carried out according to the method described in the patent, two unreacted 3,3-dimethylbutyraldehydes, APMs or two alkyl groups are introduced into the reaction mixture or the crude crystals. N- [N, N-di (3,3-dimethylbutyl) -L-α-aspartyl] -L-phenylalanine methyl ester is mixed in a considerable amount.

[0003] The sweetness of N- (3,3-dimethylbutyl) -APM and amino acid-based sweetener APM, which are high-sweetness sweeteners, is 10,000 by weight, respectively, as compared with sucrose.
0 times (Tokuhyo Hei 8-503206), about 200 times (Tokoku 47-31031)
(The weight ratio changes depending on the concentration and the type of coexisting components, etc.).

N- (3,3-dimethylbutyl) -APM
Although the details of the sweetness properties of sucrose have not been reported, the present inventors have found that the savory taste (feeling sweetness as fast as sucrose) is extremely weak, and the aftertaste (sweetness is slower than sucrose). Is extremely strong.
In addition, the astringency is strong, and the balance of sweetness is poor compared to sucrose. On the other hand, the sweetness characteristics of APM are also N
Not as good as-(3,3-dimethylbutyl) -APM,
Saki taste is weak, aftertaste is strong. Therefore, both of them have an unpleasant sweetness characteristic in which sucrose has a weak sweet taste and a strong aftertaste when making sucrose a natural sweetness.

With respect to the improvement of the sweetness characteristics of APM, various proposals have been made mainly concerning the improvement of aftertaste (for example, JP-A-56-148255, 58-141760, 58-220668, etc.).
There has also been proposed a method of obtaining a natural sweetness closer to sucrose, for example, by using sucrose in combination with APM (Japanese Patent Application Laid-Open No. 57-155282). However, according to the knowledge of the present inventor, by combining the high-sweetness sweetener N- (3,3-dimethylbutyl) -APM and the amino acid-based sweetener APM, the taste is strengthened, the aftertaste is weakened, In addition, the astringency can be reduced and the sweetness can be balanced. That is,
Weak N- (3,3-dimethylbutyl) -APM
And APM, N- (3,3-
Dimethylbutyl) -APM and APM each have an improved savory taste as compared to the case of using APM alone, and a high-intensity sweetener with a sweetness closer to sucrose that is well balanced as a whole is obtained.

[0006] The sweetness intensity of N- (3,3-dimethylbutyl) -APM, which is a sweetener having a high degree of sweetness, is 10,000 times that of sucrose in weight ratio (Tokuhyo Hei 8-503206). Difficulty adjusting sweetness during use. Therefore, the combined use of N- (3,3-dimethylbutyl) -APM and APM is preferable not only from the viewpoint of improving the sweetness, but also from the viewpoint of use.

[0007]

The object of the present invention is to provide APM and N- (3,3-dimethylbutyl)-described in the preceding section.
APM with improved sweetness in view of the sweetness characteristics of APM
And a method for producing a sweetener composition containing N- (3,3-dimethylbutyl) -APM in a simple, uniform, high-yield, high-purity manner, rather than mixing them separately after producing them. It is to provide a sweetener composition.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, N- (3,3-dimethylbutyl)
In producing APM by the reductive alkylation reaction of APM with 3,3-dimethylbutyraldehyde,
By using 3,3-dimethylbutyraldehyde not more than 1 equivalent of APM, N having two alkyl groups
-[N, N-di (3,3-dimethylbutyl) -L-α-
Aspartyl] -L-phenylalanine methyl ester is not produced as a by-product, and APM and N- (3,3-dimethylbutyl) -APM are not separately produced and then mixed, but simply, uniformly, and recovered. It has been found that a sweetener composition with high purity and a good balance of sweetness can be obtained efficiently.

[0009]

DETAILED DESCRIPTION OF THE INVENTION N- (3,3-dimethylbutyl)-
When producing APM by the reductive alkylation method of APM and 3,3-dimethylbutyraldehyde,
If dimethylbutyraldehyde is used in an amount equal to or less than 1 equivalent of APM, N- [N, N-di (3,3-dimethylbutyl) -L
-Α-aspartyl] -L-phenylalanine methyl ester was partially converted to N- (3,3
-Dimethylbutyl) -APM. After the completion of the reaction, if separation from the reducing agent is performed, N- (3,
A solution containing (3-dimethylbutyl) -APM and APM is obtained. This solution is concentrated if necessary, and after crystallization,
By separating the precipitated crystals, APM and N-
A sweetener composition containing (3,3-dimethylbutyl) -APM can be produced.

As the reducing agent used in the reaction, platinum carbon, palladium carbon, platinum black, palladium black (WO95 / 30689) and the like are known, but the type of the reducing agent is not limited to these.

Solvents used in the reaction include water, ethyl acetate, methyl acetate, acetic acid, toluene, hexane, tetrahydrofuran, acetonitrile, dimethoxyethane, ethyl ether, isopropyl alcohol, ethyl alcohol, methyl alcohol, dichloromethane, chloroform and 1,2- What is selected from dichloroethane or a mixed solvent thereof may be used.

In order to increase the yield, it is necessary to increase the APM concentration of the reaction solution for crystallization. Therefore, it is preferable to use an alcohol-based solvent or a mixed solvent of the alcohol-based solvent and another solvent for the reaction. However, when the residual solvent in the final product poses a major problem in product quality, it is preferable to use water or to use a mixed solvent of this and an alcohol-based solvent.

The post-treatment of the reaction solution is carried out by separating the reducing agent. The reaction solution obtained in this manner should be treated with water as much as possible to minimize the residual solvent in the final product when an alcohol-based solvent or a mixed solvent of this and another solvent is used for the reaction. Must be replaced. this is,
This is achieved by adding an appropriate amount of water to the reaction solution and then concentrating.

N- (3,3-dimethylbutyl) -APM and N- (3,3) in the total weight of APM of the final product
Controlling the weight ratio of (3-dimethylbutyl) -APM is based on the amount of 3,3-dimethylbutyraldehyde,
This can be achieved by adjusting the reaction temperature and the reaction time, but before the start of the reaction, an appropriate amount of APM is added to the solution or higher, and before the separation with the reducing agent, the undissolved APM is dissolved by heating or the like, or This can also be achieved by adding and dissolving an appropriate amount of APM to the reaction solution after the separation. In the present invention, not only the reaction is carried out by dissolving APM in the solvent used for the reaction, but also the APM obtained in the APM manufacturing process.
The reaction can be performed using the PM slurry or the APM solution as it is.

The reaction solution thus obtained is concentrated, if necessary, and then cooled, concentrated, neutralized, crystallized, and the like, and APM and N
A mixture containing-(3,3-dimethylbutyl) -APM may be crystallized. When the amount of APM is large, it is known that fine crystals are generated when stirring is performed.
It is desirable to carry out static crystallization as described in JP-B-03-025438, or to carry out stirring crystallization as necessary after conducting static crystallization.

A significant advantage of such a method is that N
As compared with the case where-(3,3-dimethylbutyl) -APM and APM are mixed as crystals, it is natural that a uniform mixing state is achieved.

The sherbet or slurry obtained by crystallization is subjected to solid-liquid separation and drying, or, if necessary, granulation to obtain a final product.

Examples of the method of solid-liquid separation include filtration, centrifugal separation, and drying, such as a vacuum dryer, a fluidized bed dryer, a spray dryer, and a micron dryer. Granulation methods include dry and wet granulation. However, the present invention is not limited to these.

Hereinafter, the present invention will be described in more detail with reference to examples.

(Example 1) APM containing 3.9% by weight of water
55.0 g (0.180 mol), 2 ml (0.016 mol) of 3,3-dimethylbutyraldehyde and 1000 ml of water
ml and the solution was kept at 23 ° C. To this was added 5.0 g of 5% palladium carbon, and the hydrogen flow rate was increased by 1 hour.
Reduction was performed with 00 ml for 2 hours. Thereafter, the blowing of hydrogen was stopped, the temperature was raised to 69 ° C., and all undissolved crystals were dissolved. The catalyst was removed by filtration (0.5 micrometer filter paper), and the filtrate was allowed to stand still at 5 ° C. for 4 hours for crystallization. While the obtained pseudo solid phase (sorbet) was kept at 5 ° C., stirring was performed overnight to obtain a slurry. After the obtained slurry was separated into a solid phase and a liquid phase by filtration (filter paper of 5 micrometers), the solid phase was washed with 250 ml of water. The washed solid phase was dried under reduced pressure at 50 ° C. overnight, and 43.6 g of dry crystals containing 2.7% by weight of water (measured by high performance liquid chromatography, APM: 95.8% by weight, N- ( 3,3-dimethylbutyl) -APM: 2.5
% By weight). Moreover, as a result of analyzing this by TLC,
The dialkylated product N- [N, N-di (3,3-
Dimethylbutyl) -L-α-aspartyl] -L-phenylalanine methyl ester was not included.

[0021]

According to the method of the present invention, aspartame having improved taste quality and N- (3,3-dimethylbutyl)
-APM-containing sweetener composition, aspartame and N-
Compared to separately producing (3,3-dimethylbutyl) -APM and then mixing, it can be produced simply and uniformly, with high yield and purity.

Claims (3)

[Claims] 1. N- [N- (3,3-dimethylbutyl)
-L-α-aspartyl] -L-phenylalanine methyl ester (N- (3,3-dimethylbutyl) -AP
M) is produced by the reductive alkylation reaction of aspartame with 3,3-dimethylbutyraldehyde, by using an equivalent amount or less of 3,3-dimethylbutyraldehyde to aspartame, whereby N- (3,3-dimethylbutyl) is obtained. ) -APM was partially produced from aspartame, the reaction solution was separated from the reducing agent, and after crystallization, the precipitated crystals were separated to separate aspartame and N-.
A method for producing a sweetener composition containing (3,3-dimethylbutyl) -APM. 2. APM obtained by the method according to claim 1.
And a sweetener composition containing N- (3,3-dimethylbutyl) -APM. 3. APM obtained by the method according to claim 1.
And a dry sweetener composition containing N- (3,3-dimethylbutyl) -APM.